Treatment of hydrocarbon oils



` May 2s, 1935.

lJ. MORRELL TREATMENT 0F HYDROCARBON OILS Original Filed Jan. 30, 1931 NYM WUMWN arret hz/enter: v v J ne 6'; 253/ Patented May 28, 1935 UNITED;STATES y t l l y adcaw y Y rn TREATMENT or nrnnooaaon ons Y v 4Jacque (Il.y llfor'rell,Chicago,` IIL, assigner to Unii; y. `versal Oil Products Company, Chicago, Ill., a

" "corporation o! South Dakota Applicaunuliuay'ao, 1931,` serial No. 512,475.

\ vRenewed August 23, 1933 11 emma (ci. 19e-36) substantial` desulfurization and, 'hydrogenation with resultant improvement in the `quality of the oils.- `InA the specific embodiment of tl'ie,v invention crackedhydrocarbon vapors are passed thru metalsof the alkaline or alkaline earth groups preferably in a molten :state altho the metals may be solidunder` some conditions of treatmentalong with such gasesias ammonia, steam and air, prei'-, erably the former, the resultant reactions form-- ing in part sulfides of the Ametals involved, hydrogen sulfide and hydrogen in a state suiliciently reactive `to substantially saturate the oleilnic constituents of the vapors. ,v The vapors to be treated may arise from an ordinary distillation system or from a cracking system, e. g.-the

cracked vapors fortreatment may be produced by introducing high boiling hydrocarbon oil lcharging stocks into direct contact with icracked vapors in a preliminary fractionator constituting part of, a cracking lay-out wherein heat exchange is eiected andA reux condensates mixed with raw .oil are taken by4 a 1 combined ieed pump and pumped to suitable `heating element During passage 'thru the heating element heat'is added `to initiate desired conversion reactions, the vapors-vare passed to; an enlarged lzone to permit continuance of the reactions with the separation of heavy carbonaceous residues from vapors, the latterbeing passed under reduced or differential pressuresto preliminary fractionating equipment wherein light vapors fand reflux condensates `amenable toy retreatmenty are produced. These light vapors pass to containers holding the metals which'are heated when it is desired totreat with the molten metal thru; which the vapors rise along with proportioned mixtures of ammonia,A

iied by the heavier portions -of naturally occur-l' ring-petroleums or fractions heavier than gasoline may be taken from line I containing valve 2 by pump 3 and discharged either to line l containing valve 5 or line I' containing valve 5. Line l leads to preliminary fractionator I6 in which the incoming raw oil exchanges heat with the cracked vapors andassists' in their'fractionaf, tion.,l vReiiux condensates from the Vfractionator leavethru line v Il equipped with valve il and leading to combined feed pump i9. Line 4 containing valve 5 leads also topumplll and enables direct feed of raw oil when desirable. Pump Vl! discharges to line containi'ng valve 2l, this line leading to heating elementt which may be a combination of tubular` elements constituting a continuous pipe coil disposed to receive heat from furnace 1.Y During passage thru the heating ele` ment heat may be `added t'o a degreesuiiicient to initiate desired conversion reactions, lthe heated products passing thru line 8 `containing valve 9 into enlargeclzone lilA in which the reactions are allowed to progress to` avdenite point. Temperatures at the exit of heating element Smay be of the orderof '750 to l00()I4 F. morebr less, and pressures maintained on the reaction chamber of `the order or 100 to 500 lbs. per sq. in depending upon the type of oil charged and theldegree `of conversion desired. Line Illcontaining valve l2 is provided for the removal of heavyliquid residuesfrom the process and manheadl 3 for similar removal of solid or semi-solid materials which may be produced by deeper or more intensive cracking reactions.V Vapors leave chamber I0 thrullne M equipped With valve l5 and enter preliminary fractionator I6 with or without pressure reduction over that differentialV necessary for proper conditions or `flow, reflux condensates leaving thru line Il as previously disclosed. 'I'he vapors from fractionator. i6 pass thru line 22 containing valve 23, preferably with substantial pressure reduction -to distributing means 26, which may be a perforated coil of pipe orany other suitable type of spray or nozzle adapted to produce small bubbles ofvapor. 'Treating tower 24 may consist of lowersection 25 and upper section 25'. 'I'he lower section is `adapted to c ontain metals of the alkali or alkaline earth groups, either singly or in combination, and preferably in a molten condition. As examples of metals of ,the alkali group may be mentioned sodium, `potassium,t lithium, etc. and of the alkaline earth calcium, magnesium, barium,v strontium, etc. To enable the maintenance of suitable temperature conditionsV a jacket 24 is shown which` typies any heating'means thatmay be employed; line 33 containing valve 34 -serving for the adxnissiony P-ATENT OFFICES] taining valve 32 for the introduction of air. The reactions' occurring in the lower section 25 of treating tower are characteristic of the invention and result in substantial desulfurization and hydrogenation of the cracked vapors. -Thle reactions of ammonia with metals of the groups mentioned are of Aa nature dependent upon the reactivity of the metals in the groups and vary from those resulting in the disruption of the ammonia. radical to produce free hydrogen and 'amides as in the case of s'odium, to reactions of simple addition of the ammonia. molecule to the metal as occurs in the case of calcium, which adds four molecules of ammonia to one atom of calcium. Depending upon conditions, imides may also be formed with progressive liberation ofhydrogen and by the introduction of regulated quantities of steam and air still further amounts of hydrogen may be liberated, thus tending to increase the rate of hydrogenating reactions. 'I'he metals themselves may react to some extent with the sulfur compounds toy produce their correspondingsuliides. By employing varying mixtures of the` metals of the two groups masses of varyingfluidity and reactivity may be provided suitable for the treatment of'particular vapors. For example, if thev reaction is violentV or explosive when sodium alone is used, a certain amount of calcium or other alkaline kearthfmetals may serve to moderate the speed of the reaction and bring it vwithin controllable limits. vVice versa the sodium may be used to lower the melting point of the calcium. The vapors from the treating compartment 25 may pass to-the upper portion 25 of tower 24 which .contains fractionating devices not shown, such as bubble trays, and vapors of desired boiling point range may therein be produced, these passing thru line 39 containing valve 40 to condenser 4I wherein partial liquefaction is effected, the cooled products passing thru line 42 containing valve 43 into receiver 44 which is equipped with line 45 containing valve 46 for the removal "of xed gases and line 41 containing valve 48 to permit the withdrawal yof liquids of desired boiling point range to suitable storage.

Similarly, hydrocarbon vapors from any source may be treated in a suitable contacting or treating device, such as va vessel or tower permitting contact betweenA the vapors and the reagents.

It is evident from the foregoing description that the process of the invention comprises the treatment of a wide variety of cracked vapors under conditions of` sufficient latitude to enable their Yeffective transformation into liquids of a high degree of refinement. While one typical operation hasbeen shown, it is only one of many that may be employed land as such is not to be construed in the limiting sense upon the wide scope of Vthe invention. y

As an example of the results obtainable by the operation of the process of the invention a 24.

A. P.' I. gravity topped crude typical of the Mid- Continent producing'area may be cracked in apparatus similar to that described above to produce approximately 65% yield'of motor' fuel with an A. P. I. gravity of approximately 56, a gum content of approximately l mg. by thecopper dish method, a Sulfur content of less than approximately 0.1% anda color of above 30 on the system shows these results. When the operation is conducted without the treating method characteristic of the process of the invention, the gasoline produced will be of a considerably less rened nature and may run as high as 300 mg. of

gum per 100 cc. and have a sulfur content as high as 0.25%. This comparison is sulcient to indicate that results of great commercial value are obtainable by the operation of the process. Likewise a cracked. distillate showing a gum content of approximately 600 mg. per 100 cc. and a sulfur content of about 0.6% may be distilled thru a column containing a mixture of sodium and calcium or calcium alone'introducing ammonia during the treatment and a product containing a low gum content and a sulfur content of approximately 0.20% may be obtained.

, I claim as my invention:

l. In the refining of cracked hydrocarbon vapors, the step which comprises passing the vapors with ammonia gas through molten alkalinous metal.

2. In the rening of cracked hydrocarbon vapors, the step which comprises passing the vapors with ammonia gas through molten alkali metal.

3. In the refining of cracked hydrocarbon vapors, the step which comprises passing the vapors with ammonia gas through a. molten mixture of an alkali metal and an alkaline earth metal.

4. In the rening of cracked hydrocarbon vapors, the step which comprises passing the vapors with ammonia gas through a mixture of molten sodium and calcium.

5. In the refining ofcracked hydrocarbon vapors, the step which comprises passing the vapors with ammonia gas and steam through molten alkalinous metal.

6. In the refining of cracked hydrocarbon vapors, the step which comprises passing the vapors with ammonia gas, steam and air through molten alkalinous metal.

' 7. A process for refining cracked distillates containing olens and sulphur which comprises treating the distillate in vapor phase simultaneously with ammonia gas and an alkalinous metal Vat a temperature adequate to react the ammonia with the metal.

8. A process for refining cracked distillates containing oleflns and sulphur which comprises treating the distillate in vapor phase and in the presence of steam simultaneously with ammonia. gas and an alkalinous metal at a temperature adequate to react the ammonia with the metal.

9. A process for refining cracked distillates containing olens and sulphur which comprises treating the distillate in vapor phase simultaneously with ammonia gas and an alkali metal at a temperature adequate to react the ammonia with the metal. A

10. A process for rening cracked distillates containing olens and sulphur whichv comprises treating the distillate in vapor phase simultaneously with ammonia gas and an alkaline earth metal at a temperature adequate to react the arnmonia with the metal.v

11. Avprocess for reiining cracked distillates containing olefins and sulphur which comprises treating the distillate in vapor phase simultaneously with ammonia gas and a mixture of an alkali metal and an alkaline earth metal at a P temperature adequate to react the ammonia with at least one of said metals.

` JACQUE C. MORRELL. 

